L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水 制备5-羟甲基糠醛

doi:10.11949/j.issn.0438-1157.20160115

化工学报 ›› 2016, Vol. 67 ›› Issue (7): 2799-2807.DOI: 10.11949/j.issn.0438-1157.20160115

• 催化、动力学与反应器 • 上一篇下一篇

L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水制备5-羟甲基糠醛

苏叶, 鲍宗必, 张治国, 邢华斌, 杨启炜, 苏宝根, 杨亦文, 任其龙

浙江大学化学工程与生物工程学院, 生物质化工教育部重点实验室, 浙江杭州 310029

收稿日期:2016-01-26 修回日期:2016-03-21 出版日期:2016-07-05 发布日期:2016-07-05
通讯作者: 鲍宗必
基金资助:
国家自然科学基金项目（21436010，21376205）。

Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF

SU Ye, BAO Zongbi, ZHANG Zhiguo, XING Huabin, YANG Qiwei, SU Baogen, YANG Yiwen, REN Qilong

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310029, Zhejiang, China

Received:2016-01-26 Revised:2016-03-21 Online:2016-07-05 Published:2016-07-05
Supported by:
supported by the National Natural Science Foundation of China (21436010, 21376205).

摘要/Abstract

摘要：

以九水合硝酸铬和单磺酸钠对苯二甲酸为原料，水为溶剂，采用水热法合成系列磺酸功能化MIL-101（Cr），通过调节反应温度和时间，合成不同Lewis/Brönsted催化位点比例的磺酸功能化MIL-101（Cr），采用PXRD、EDX、SEM、ICP-AAS及BET比表面积分析等技术对材料进行综合表征，并研究磺酸功能化MIL-101（Cr）催化葡萄糖脱水制备5-羟甲基糠醛的催化活性。催化反应动力学研究结果表明，MIL-101（Cr）-SO₃H中的Cr（Ⅲ）作为葡萄糖异构化反应的Lewis酸位点，－SO₃H作为果糖脱水反应的Brönsted酸催化位点，当催化剂的Brönsted酸和Lewis酸的摩尔比为1.1时，150℃下反应，5-羟甲基糠醛的选择性最高可以达到47.15%，5-羟甲基糠醛的产率最高达到46.0%。

关键词: 金属有机骨架材料, 催化, 葡萄糖, 5-羟甲基糠醛, 反应动力学

Abstract:

A series of Cr-terephthalates metal-organic frameworks functionalized by sulfonic acid group (-SO₃H) [MIL-101(Cr)-SO₃H], featuring varied ratios of Lewis acid site to Brönsted acid site, were synthesized by hydrothermal reaction method starting from Cr(NO₃)₃·9H₂O and sodium 2-sulfoterephthalate under various conditions of temperature and reaction time. The catalysts were characterized by techniques of PXRD, EDX, SEM, ICP-AAS and BET surface area, and the catalytic performances for glucose conversion to 5-HMF were evaluated. It showed that, in terms of the catalysis kinetics, Cr³⁺ serves as the Lewis acid sites of MIL-101(Cr)-SO₃H for glucose isomerization, and sulfonic acid group, the Brönsted acid site for the fructose dehydration. The highest HMF selectivity of 47.15% and the highest HMF yield of 46.0% was achieved under conditions of molar ratio of Brönsted acid site to Lewis acid site of 1.1, 150℃ for 2 h.

Key words: metal-organic framework, catalysis, glucose, 5-hydroxymethyl furfural, reaction kinetics

中图分类号:

O643.36

苏叶, 鲍宗必, 张治国, 邢华斌, 杨启炜, 苏宝根, 杨亦文, 任其龙. L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水制备5-羟甲基糠醛[J]. 化工学报, 2016, 67(7): 2799-2807.

SU Ye, BAO Zongbi, ZHANG Zhiguo, XING Huabin, YANG Qiwei, SU Baogen, YANG Yiwen, REN Qilong. Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF[J]. CIESC Journal, 2016, 67(7): 2799-2807.

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L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水制备5-羟甲基糠醛

Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF

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L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水 制备5-羟甲基糠醛

Sulfonic acid functionalized MIL-101(Cr) catalysts with tunable Lewis acid and Brönsted acid sites for glucose dehydration to 5-HMF

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L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水制备5-羟甲基糠醛